Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
  • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
  • C07D491/04—Ortho-condensed systems

Definitions

• This invention relates to novel and therapeutically valuable compounds of the formula: ##SPC2##
• each of X 1 and X 2 is a hydrogen atom, a halogen atom (e.g. F, Cl or Br), an alkyl group having 1 to 4 carbon atoms (e.g. methyl, ethyl, propyl or butyl) or an alkoxy group having 1 to 4 carbon atoms (e.g. methoxy, ethoxy, propoxy or butoxy); each of R 1 and R 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (e.g.
• A is a carbonyl group, a methylene group or an alkylidene group having 2 to 4 carbon atoms (e.g. ethylidene, propylidene, isopropylidene or butylidene);
• Y is --O--, --S-- or --N(R)-- [wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (e.g.
• Z is OH or Q--B--N(R 3 )(R 4 ) [wherein Q is 0 (oxygen a atom) or MH, B is an alkylene group having 1 to 4 carbon atoms (e.g. methylene, ethylene, trimethylene, propylene or tetromethylene) and each of R 3 and R 4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (e.g.
• R 3 and R 4 together with the adjacent nitrogen atom form a saturated hetorocycle selected from the group consisting of pyrrolidine, piperidine, morpholine, piperazine and piperazine substituted by an alkyl group having 1 to 4 carbon atoms at the 4-position (e.g. 4-methylpiperazine, 4-ethylpiperazine, 4-propylpiperazine or 4-butylpiperazine)], and ring P represents a pyridine or a pyridine N-oxide ring.
• n 0 (zero) or 1. They are useful as antirheumatics, analgesics, antipyretics and anti-inflammatory agents.
• the compounds of formula [I] can be produced, for example, by the following methods:
• W 1 is a functional group hydrolyzable into COOH [e.g. COOR 5 (wherein R 5 is an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl or butyl), ##EQU1## in a conventional manner.
• COOR 5 wherein R 5 is an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl or butyl
• the hydrolysis is advantageously carried out in a solvent (e.g. water, aqueous methanol, aqueous dioxane or acetic acid) in the presence of an acid (e.g. hydrochloric acid or sulfuric acid) or an alkali (e.g. sodium hydroxide or potassium hydroxide), usually under reflux.
• a solvent e.g. water, aqueous methanol, aqueous dioxane or acetic acid
• an acid e.g. hydrochloric acid or sulfuric acid
• an alkali e.g. sodium hydroxide or potassium hydroxide
• the compound of formula [III] is hydrolyzed, advantageously under alkaline conditions with sodium hydroxide or potassium hydroxide, to give a corresponding malonic acid, and the thus-obtained malonic acid derivative is decarboxylated under neutral or acid conditions; or the compound of formula [III] is hydrolyzed and decarboxylated at the same time under acid conditions with hydrochloric or sulfuric acid.
• the reaction is usually carried out under reflux.
• the oxidation is advantageously carried out in a solvent (e.g. acetic acid, propionic acid, acetone, dioxane, water or a mixture of water and any of the said solvents) in the presence of an oxidizing agent (e.g. nitric acid, halogen, hydrogen peroxide, copper hydroxide, selenium dioxide, chromic anhydride, dichromate, permanganata, silver oxide, organic peracid or hypochlorous ester) at 0°-80°C.
• a solvent e.g. acetic acid, propionic acid, acetone, dioxane, water or a mixture of water and any of the said solvents
• an oxidizing agent e.g. nitric acid, halogen, hydrogen peroxide, copper hydroxide, selenium dioxide, chromic anhydride, dichromate, permanganata, silver oxide, organic peracid or hypochlorous ester
• R 6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (e.g. methyl, ethyl, propyl or butyl), in a conventional manner.
• a conventional reduction e.g. Wolff-Kishner reduction, Haung-Minlon modification thereof, Clemensen reduction, catalytic reduction under a catalyst such as nickel, palladium or platinum, reduction by the use of sodium borohydride or reduction by the use of of red phosphorus and hydriodic acid, can be applied.
• the compound of formula [VI] can also be reduced only by heating, advantageously in the presence of an acid, to give the compound of formula [I] wherein A is a methylene group.
• the reduction is usually carried out in a solvent (e.g. methanol, ethanol, isopropyl alcohol, dioxane or water) at 10°-100°C for a period of from 1 to 10-odd hours.
• a solvent e.g. methanol, ethanol, isopropyl alcohol, dioxane or water
• R 7 and R 8 are as defined above, and each of R 7 and R 8 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (e.g. methyl, ethyl or propyl). The sum of carbon atoms of R 7 and R 8 is not more than 3.
• a conventional hydrogenation e.g. catalytic hydrogenation under a catalyst such as nickel, palladium or platinum of hydrogenation by the use of red phosphorus and hydriodic acid, can be applied.
• W 3 is a hydroxyl group, a halogen atom (e.g. Cl or Br) or a residue or an amine (e.g. dimethylamino, piperidino or morpholino).
• a conventional hydrogenolysis e.g. catalytic hydrogenolysis under a catalyst such as nickel, palladium or platinum, hydrogenolysis by the use of metal and acid (e.g. zinc-acetic acid) or hydrogenolysis by the use of red phosphorus and iodine, can be applied.
• a catalyst such as nickel, palladium or platinum
• metal and acid e.g. zinc-acetic acid
• red phosphorus and iodine e.g. red phosphorus and iodine
• X 1 , X 2 , R 1 , R 2 , Y and P are as defined above, A' is a methylene group or an alkylidene group having 2 to 4 carbon atoms and W 4 is a lithium atom or a residue of a Grignard reagent.
• X 1 , X 2 , R 1 , A and P are as defined above, either Y 1 or Y 2 is Y--H [wherein Y is as defined above], and the other is a halogen atom (e.g. Cl, Br or I).
• the condensation is advantageously carried out in the presence of a hydrochloride or a sulfate or pyridine, quinoline or picoline at 100°-250°C.
• the condensation is carried out with or without a solvent (e.g. benzene, nitrobenzene or dichloroethane) in the presence of a condensing agent (e.g. polyphosphoric acid, phosphoric anhydride, sulfuric acid, aluminum chloride, acetic anhydride, boron trifluoride or hydrogen chloride) at about 20° to 150°C.
• a solvent e.g. benzene, nitrobenzene or dichloroethane
• a condensing agent e.g. polyphosphoric acid, phosphoric anhydride, sulfuric acid, aluminum chloride, acetic anhydride, boron trifluoride or hydrogen chloride
• R 9 is an alkyl group having 1 to 4 carbon atoms (e.g. methyl, ethyl, propyl or butyl), and Q 1 is a halogen atom (e.g. Cl, Br or I) or an alkyl- or aryl-sulfonyloxy (e.g. p-tolylsulfonyloxy or methylsulfonyloxy).
• Q 1 is a halogen atom (e.g. Cl, Br or I) or an alkyl- or aryl-sulfonyloxy (e.g. p-tolylsulfonyloxy or methylsulfonyloxy).
• the reaction is advantageously carried out in an inert solvent (e.g. benzene, toluene, xylene, tetrahydrofuran, dimethyl sulfoxide or liquid ammonia) in the presence of an alkaline condensing agent (e.g. sodium methoxide, sodium ethoxide, sodium amide, potassium amide or sodium hydride) at about -35° to 150°C.
• an inert solvent e.g. benzene, toluene, xylene, tetrahydrofuran, dimethyl sulfoxide or liquid ammonia
• an alkaline condensing agent e.g. sodium methoxide, sodium ethoxide, sodium amide, potassium amide or sodium hydride
• Q 2 is OH, NH 2 , or a halogen atom (e.g. Cl or Br) or an alkyl- or aryl-sulfonyloxy (e.g. p-tolylsulfonyloxy or methylsulfonyloxy), with the compound of formula [I] wherein Z is OH or its reactive derivative appropriately selected.
• a halogen atom e.g. Cl or Br
• an alkyl- or aryl-sulfonyloxy e.g. p-tolylsulfonyloxy or methylsulfonyloxy
• the reactive derivative of the compound of formula [I] wherein Z is OH is, for example, a metal salt (e.g. sodium salt, potassium salt, calcium salt), an acid halide, an acid anhydride or a lower alkyl ester (e.g. methyl ester, ethyl ester, propyl ester or isopropyl ester).
• a metal salt e.g. sodium salt, potassium salt, calcium salt
• an acid halide e.g. sodium salt, potassium salt, calcium salt
• an acid halide e.g. sodium salt, potassium salt, calcium salt
• an acid halide e.g. sodium salt, potassium salt, calcium salt
• an acid halide e.g. sodium salt, potassium salt, calcium salt
• an acid halide e.g. sodium salt, potassium salt, calcium salt
• an acid halide e.g. sodium salt, potassium salt, calcium salt
• an acid halide e.g. sodium salt, potassium salt, calcium salt
• the reaction is carried out in a conventional manner.
• a solvent e.g. benzene, toluene, xylene or chloroform
• an acid catalyst such as sulfuric acid or p-toluenesulfonic acid.
• R 3 and R 4 are as defined above.
• the reaction is usually carried out in an inert solvent (e.g. benzene, toluene, acetone, dimethylformamide, dioxane or ethanol) at about 20° to 150°C, optionally in the presence of a condinsing agent (e.g. organic base such as pyridine, quinoline or picoline or inorganic base such as potassium carbonate or sodium carbonate).
• an inert solvent e.g. benzene, toluene, acetone, dimethylformamide, dioxane or ethanol
• a condinsing agent e.g. organic base such as pyridine, quinoline or picoline or inorganic base such as potassium carbonate or sodium carbonate.
• [XVII] is reduced to [XVIII], for example, by the method described in Journal of the Chemical Society, 1952, pages 2057-62; [XVIII] is heated in the presence of an acid to give [XIX]; [XIX] is methylated with methyl iodide in the presence of an alkalline condensing agent such as sodium amide to give [XX].
• an alkalline condensing agent such as sodium amide
• A' is a methylene group or an alkylidene group having 2 to 4 carbon atoms.
• [XXI] is chloromethylated with hydrogen chloride and formaldehyde to give [XXII]; [XXII] is allowed to react with potassium cyanide or cuprous cyanide in a solvent (e.g. dimethylformamide or dimethyl sulfoxide) to give [IIa]; [IIa] is allowed to react with diethyl carbonate and methyl iodide in the presence of sodium methoxide to give [IIIa]; [IIIa] is decarboxylated under reflux to give [IIb]; [IIb] is allowed to react with ethanol in the presence of a concentrated sulfuric acid to give [IIc]. ##SPC18##
• [XXIII] is brominated with N-bromosuccinimide (N.B.S.) to give [XXIV]; [IId] and [IIIb] are derived from [XXIV] by the method mentioned above; methylation of [IId] with methyl iodide in the presence of an alkalline condensing agent gives [IIe]. ##SPC19##
• [XXV] is acetylated with acetyl chloride or acetic anhydride in the presence of a catalyst such as anhydrous aluminum chloride to give [XXVI]; [XXVI] is subjected to Darzens' condensation to give [XXVII]; [XXVII] is hydrolyzed, and the resultant acid is decarboxylated by heating in an aqeuous or alcoholic solvent in the presence of an acid to give [IVa].
• a catalyst such as anhydrous aluminum chloride
• [XXV] is allowed to react with ethoxalyl chloride in the presence of aluminum chloride to give [XXVIII]; [XXVIII] is hydrolyzed, and the resultant acid is subjected to Grignard reaction with methyl magnesiumm iodide to give [VIIIa]; [VIIIa] is dehydrated with sulfuric acid to give [VIIa].
• [SPC21] is allowed to react with ethoxalyl chloride in the presence of aluminum chloride to give [XXVIII]; [XXVIII] is hydrolyzed, and the resultant acid is subjected to Grignard reaction with methyl magnesiumm iodide to give [VIIIa]; [VIIIa] is dehydrated with sulfuric acid to give [VIIa].
• the compounds of formula [I] wherein Z is OH can be converted in a conventional manner into the corresponding metal salts (the metal being for example Na, K, Ca, Mg or Al), the corresponding ammonium salts or the corresponding addition salts with organic bases such as triethylamine, diethylamine, morpholine or piperazine, and the compound of formula [I] wherein Z is Q--B--N(R 3 )(R 4 ) can be converted in a conventional manner into the corresponding acid addition salts with various inorganic or organic acids such as hydrochloric, hydrobromic, sulfuric, phosphoric, nitric, methanesulfonic, p-toluenesulfonic, acetic, oxalic, maleic, fumaric, citric or camphorsulfonic acid.
• the metal salts the metal being for example Na, K, Ca, Mg or Al
• the corresponding ammonium salts or the corresponding addition salts with organic bases such
• the compounds of formula [I] and pharmaceutically acceptable salts thereof have analgesic and anti-inflammatory actions as shown, for example, by the following tests; in which the alphabetical notations A to D mean the following compounds, respectively:
• guinea pigs weighing 250-450 g, a rubber plate with 3 holes of 7 mm in diameter was fitted to the abdomen, hair of which had been removed in advance, and light was given by a mercury lamp (300 W, Tokyo Shibaura Electric Co., Ltd.) at the distance of 15 cm for 150 seconds. Two hours later the degree of erythema formation was marked according to the method of Winder et al. (Arch. Intern. Pharmacodyn., 116, 261 (1958)) and the efficacy rate was calculated, based on the criterion that 1.5 or less of total marks be effective. Half amount of the test solution was orally given 1 hour before and after the irradiation.
• the compounds of formula [I] in accordance with the invention and pharmaceutically acceptable salts thereof can be administered safely as anthirheumatics, analgesics, antipyretics and anti-inflammatory agents, either alone or in the form of a pharmaceutical composition consisting essentially of a therapeutically effective amount of the compound in admixture with a suitable and conventional carrier or adjuvant, administrable orally, percutaneously or by way of injection, without harm to the host.
• the pharmaceutical composition can take the form of tablets, granules, powder or capsules, for oral administration, of injectable solution for subcutaneous or intramuscular administration, or of cream, ointment, jelly or suppository for topical administration.
• the choice of carrier is determined by the preferred form of administration, the solubility of the compounds and standard pharmaceutical practice.
• the tablets may be sugar-coated in a conventional manner.
• the usual daily dose of compound [A] or a salt thereof lies in the range of about 50-100 milligrams per human adult.
• a solution of 11.5 g of 7-cyanomethyl-5H-[1]benzopyrano[2,3-b]-pyridine in a mixture of 60 ml of acetic acid and 25 ml of concentrated hydrochloric acid is heated under reflux for 24 hours. After concentration, water is added to the residue, and further 10% sodium hydroxide solution is added to dissolve the residue. An insoluble material is removed by extraction with chloroform. The aqueous layer is made acid with acetic acid, and the resulting crystalline precipitate is filtered off. The crystals are recrystallized from dioxane to give 8.5 g of 5H-[1]benzopyrano[2,3-b]-pyridin-7-yl-acetic acid as white needles melting at 218°C.
• the above objective compound can also be produced from 7-acetyl-5H-[1]benzopyrano[2,3-b]pyridine. Namely, the acetyl compound is subjected to Willgerodt reaction, and the thioamide compound obtained is hydrolyzed with potassium hydroxide in isopropyl alcohol.
• 5-Hydroxy-5H-[1]benzopyrano[2,3-b]pyridine is prepared from 5-oxo-5H-[1]benzopyrano[2,3-b]pyridine by the method described in Journal of the Chemical Society, 1952, pages 2057-62.
• a mixture of 10 g of 5-hydroxy-5H-[1]benzopyrano[2,3-b]pyridine, 100 ml of isopropyl alcohol and 10 ml of 20% hydrochloric acid in isopropyl alcohol is refluxed for 3 hours, and the reaction mixture is allowed to stand overnight.
• the isopropyl alcohol is distilled off under reduced pressure, an aqueous carbonate solution is added to the residue, and then the mixture is extracted with chloroform.
• the chloroform layer is dried, and the chloroform is distilled off.
• the residue is recrystallized from isopropyl alcohol to give 7.5 g of 5H-[1]benzopyrano[2,3-b]pyridine as white crystals melting at 87°-88°C.
• Hydrogen chloride gas is passed through a mixture of 10 g of 5H-[1]-benzopyrano[2,3-b]pyridine, 1.4 g of paraformaldehyde, 110 ml of concentrated sulfuric acid and 22 ml of concentrated hydrochloric acid at 80°C for 12 hours, while 2 g of paraformaldehyde is added in several portions to the reaction mixture.
• the reaction mixture is poured into water, and the whole mixture is neutralized with sodium carbonate, and extracted with a large amount of chloroform.
• the chloroform layer is dried, concentrated to 30 ml, and cooled.
• the resulting crystalline precipitate is filtered off, and recrystallized from chloroform to give 7-chloromethyl-5H-[1]benzopyrano[2,3-b]pyridine melting at 172°-174°C.
• a solution of 7.8 g of potassium cyanide in 20 ml of water is added dropwise to a mixture of 23 g of 7-chloromethyl-5H-[1]benzopyrano[2,3-b]-pyridine and 200 ml of dimethylformamide.
• the mixture is allowed to stand at 55°-60°C for 2 hours, and then poured into a large amount of water.
• the resulting crystalline precipitate is filtered off, washed with water, and recrystallized from aqueous dioxane to give 20 g of 7-cyanomethyl-5H-[1]-benzopyrano[2,3-b]pyridine melting at 166°-167°C.
• aqueous layer is made acid with acetic acid, and the resulting crystalline precipitate is filtered off and recrystallized from aqueous dimethylformamide to give 8.6 g of 5-oxo-5H-[1]benzopyrano[2,3-b]pyridin-7-yl-acetic acid as white needles melting at 244°- 245°C.
• the above objective compound can also be produced from 7-acetyl-5-oxo-5H-[1]benzopyrano[2,3-b]pyridine. Namely, the acetyl compound is subjected to Willgerodt reaction, and the thioamide compound obtained is hydrolyzed with potassium hydroxide in isopropyl alcohol.
• a mixture of 42 g of 7-methyl-5-oxo-5H-[1]benzopyrano[2,3-b]pyridine, 36 g of N-bromosuccinimide, 0.4 g of benzoyl peroxide and 420 ml of carbon tetrachloride is refluxed with stirring under ultraviolet light for 2 hours.
• the reaction mixture is filtered rapidly while it is hot.
• the crystals thus obtained are suspended in hot water (about 60°C).
• the suspension is stirred thoroughly, and filtered.
• the crystals are recrystallized from dioxane to give 47.1 g of 7-bromomethyl-5-oxo-5H-[1]benzopyrano[2,3-b]-pyridine melting at 211°-212.5°C.
• a mixture of 3 g of ethyl 2-(5H-[1]benzothiopyrano[2,3-b]pyridin-7-yl)propionate and 0.48 g of sodium hydroxide is dissolved in a mixture of 25 ml of ethanol and 5 ml of water, and the solution is heated under reflux for 1.5 hours. The ethanol is distilled off under reduced pressure, and water is added to the residue.
• a mixture of 3.1 g of ethyl 2-(5-oxo-5H-[1]benzothiopyrano[2,3-b[-pyridin-7-yl)propionate and 0.48 g of sodium hydroxide is dissolved in a mixture of 25 ml of ethanol and 5 ml of water. The solution is heated under reflux for 1 hour. The ethanol is distilled off under reduced pressure, and the residue is dissolved in water.
• a solution of 0.76 g of metallic sodium in 15 ml of ethanol is added to a mixture of 6.6 g of 7-cyanomethyl-5H-[1]benzopyrano[2,3-b]pyridine and 46 ml of diethyl carbonate, and the whole mixture is refluxed for 1 hour.
• 5.2 g of methyl iodide is added to the reaction mixture.
• the temperature of the mixture is raised gradually, and the mixture is refluxed for 2 hours.
• the excess diethyl carbonate is distilled off, and toluene is added to the residue.
• the mixture is washed with water, and the toluene layer is dried.
• the aqueous layer is made acid with acetic acid, and the crystalline precipitate is collected and recrystallized from aqueous dioxane to give 11 g of 2-(5-oxo-5H-[1]benzopyrano[2,3-b]pyridin-7-yl)propionic acid as white needles melting at 194°-195°C.
• a solution of 0.75 g of metallic sodium in 16 ml of ethanol is added to a mixture of 7 g of 7-cyanomethyl-5-oxo-5H-[1]benzopyrano[2,3-b]-pyridine and 55 ml of diethyl carbonate with stirring, and the mixture is stirred under reflux for 2 hours.
• a solution of 5.2 g of methyl iodide in 5 ml of ethanol is added to the reaction mixture, and the whole mixture is stirred under reflux for 2 hours.
• the ethanol and the excess diethyl carbonate are distilled off under reduced pressure, and the residue is dissolved in toluene.
• a mixture of 3.7 g of zinc, 0.22 g of mercuric chloride, 0.22 ml of concentrated hydrochloric acid and 3.7 ml of water is stirred for 5 minutes, and the aqueous solution is removed by decantation.
• To the zinc amalgam thus obtained are added 6 ml of dioxane and 6 ml of concentrated hydrochloric acid.
• 1.5 g of 2-(5-oxo-5H-[1]benzothiopyrano[2,3-b]pyridin-7-yl)propionic acid is added to the mixture with stirring at 50°-60°C over a period of about 15 minutes.
• the whole mixture is stirred at 60°C for 1 hour.
• the excess zinc is removed by filtration, and the filtrate is evaporated under reduced pressure.
• a Grignard reagent is prepared from 0.31 g of metallic magnesium and 2.9 g of 7-(1-bromoethyl)-5H-[1]benzopyrano[2,3-b]pyridine in 10 ml of anhydrous tetrahydrofuran. To the Grignard reagent is added a large excess of dry ice. The mixture is allowed to stand overnight, and then poured into diluted hydrochloric acid. The precipitate is filtered off, and added to an aqueous sodium bicarbonate solution. An insoluble material is removed by filtration, and the filtrate is made acid with acetic acid.
• a solution of 2 g of aluminum isopropoxide in 30 ml of isopropyl alcohol is added dropwise to a solution of 2.7 g of 2-(5-oxo-5H-[1]benzopyrano[2,3-b]pyridin-7-yl)propionic acid in 100 ml of isopropyl alcohol with stirring.
• the addition is accompanied by immediate formation of white crystals.
• the mixture is stirred under reflux for 1 hour, and 20 ml of water is added to the reaction mixture, and then the whole mixture is refluxed for an additional hour.
• the chloroform layer is washed with water, dried over anhydrous magnesium sulfate, and concentrated.
• the residual oil is dissolved in 30 ml of isopropyl alcohol, and the solution is adjusted to pH 1-2 by addition of 20% alcoholic hydrochloric acid. After cooling, the crystalline precipitate is filtered off, and high vacuum dried to give 4.2 g of 2-dimethylaminoethyl 2-(5H-[1]benzopyrano[2,3-b]pyridin-7-yl)propionate hydrochloride melting at 167°-169°C.

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• 1973
  • 1973-07-11 GB GB3316173A patent/GB1403487A/en not_active Expired
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  • 1973-07-16 CH CH755176A patent/CH588487A5/xx not_active IP Right Cessation
  • 1973-07-16 CA CA176,486A patent/CA994348A/en not_active Expired
  • 1973-07-18 US US05/380,415 patent/US3931205A/en not_active Expired - Lifetime
  • 1973-07-19 FR FR7326454A patent/FR2193593B1/fr not_active Expired
  • 1973-07-19 NL NLAANVRAGE7310050,A patent/NL174551C/xx not_active IP Right Cessation
  • 1973-07-20 AR AR249194A patent/AR210720A1/es active
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